Photo-stable cosmetic or dermatological compositions

ABSTRACT

Disclosed is the use of an effective photo-stabilizing amount of stabilizing agent (a) selected from
     a diphenylacrylate UV filter (a 1 ),   a benzylidene cmphor derivative (a 2 ),   an organosiloxane comprising benzalemalonate groups (a 3 ),   a fluoren derivative (a 4 ), and   a naphthalene dicarboxylic acid derivative (a 5 )   for improving the stability with respect to UV radiation of a cosmetic or dermatological composition comprising a UV filter combination of at least one dibenzoylmethane derivative (b) and of at least one specific amino-substituted 2-hydroxybenzophenone derivative (c).

This application is a divisional of U.S. application Ser. No.11/663,610, granted which is a national stage of PCT/EP 05/054641, filedSep. 19, 2005, the contents of both herein incorporated entirely byreference.

The present invention relates to the use of a specific stabilizing agent(a) for improving the stability with respect to UV radiation of acosmetic or dermatological composition comprising a UV filtercombination of at least one dibenzoylmethane derivative (b) and of atleast one specific amino-substituted 2-hydroxybenzophenone derivative(c).

It has long been known that prolonged exposure to UV radiation can leadto the formation of erythemas or light dermatoses, as well as to anincreased incidence of skin cancers or accelerated skin ageing.

Various sunscreen formulations have been proposed which includematerials which are intended to counteract UV radiation, therebyinhibiting the said undesired effects on the skin.

A great number of compounds have been proposed for use as UV protectantsin sunscreen formulations.

In this respect, a particular advantageous family of UV-A screeningagents is currently composed of dibenzoylmethane derivatives and inparticular 4-tert-butyl-4′-methoxydibenzoylmethane; this is becausethese derivatives exhibit a high intrinsic absorbance. Dibenzoylmethanederivatives are well known per se as screening agents actives in theUV-A region, and are disclosed in particular in FR-A-2 326 405, FR-A-2440 933 and EP-A-0 114 607. Furthermore,4-tert-butyl-4′-methoxydibenzoylmethane is currently offered for saleunder the trademark of “Parsol 1789” by DSM.

Unfortunately, it is found that dibenzoylmethane derivatives arerelatively sensitive to UV radiation (in particular UV-A radiation), ANDmore specifically, that they have an unfortunate tendency to more orless rapid decomposition under the effect of the latter. Thus, thissubstantial lack of photochemical stability of dibenzoylmethanederivatives with respect to UV radiation does not make it possible toguarantee constant protection during prolonged exposure to the sun, sothat repeated sun screen applications at regular and frequent intervalshave to be carried out by the user in order to obtain effectiveprotection of the skin against UV radiation.

The photostabilization of dibenzoylmethane derivatives with respect toUV radiation constitutes a problem, which has not yet been solved untilnow in a completely satisfactory manner.

In U.S. Pat. No. 6,699,461 it is suggested to improve the photochemicalstability of dibenzoylmethane derivatives containing cosmetic ordermatological compositions with specific amino-substituted2-hydroxybenzophenone derivatives. These compositions do not comprisep-methylbenzylidenecamphor.

Unfortunately, the addition of a 2-hydroxybenzophenone derivative incosmetic or dermatological compositions photo-stabilizes thedibenzoylmethane derivative but simultaneously destabilizes the2-hydroxybenzophenone derivative.

Surprisingly it was found, that the addition of specific amounts of aspecific stabilizing agent will significantly improve the photostabilityof cosmetic or dermatological compositions comprising the combination of2-hydroxybenzophenone and dibenzoylmethane derivatives.

Therefore, the present invention relates to the use of an effectivephoto-stabilizing amount of stabilizing agent (a) selected from

a diphenylacrylate UV filter (a₁),a benzylidene camphor derivative (a₂),an organosiloxane comprising benzalemalonate groups (a₃),a fluoren derivative (a₄),a naphthalene dicarboxylic acid derivative (a₅)a natural occurring stabilizer (a₆); anda phenolic antioxidant (a₇);for improving the stability with respect to UV radiation of a cosmeticor dermatological composition comprising a UV filter combination of atleast one dibenzoylmethane derivative (b) and of at least one specificamino-substituted 2-hydroxybenzophenone derivative (c).

The diphenylacrylate UV filter (a₁) which is used in the presentinvention for the stabilization of cosmetic or dermatologicalcomposition is preferably selected from 2-ethylhexyl2-cyano,3,3-diphenylacrylate which corresponds to the formula

Suitable benzylidene camphor derivatives (a₂) are disclosed in U.S. Pat.No. 5,605,680.

Preferably, p-methylbenzylidene camphor is used in the present inventionas component (a₂).

The organosiloxane comprising benzalemalonate groups (a₃) preferablycorrespond to the formula

wherein

-   R is C₁-C₁₀alkyl; phenyl; or 3,3,3-trifluoropropyl, at least 80% of    the number of the R radicals being methyl radicals;-   r is an integer from 0 to 200;-   s is an integer from 0 to 50-   u is an integer from 1 to 20;-   t is an integer from 0 to 20; wherein t+u is equal to or greater    than 3; and.

A and/or B is a benzalmalonate radical.

A is preferably the radical of formula

wherein

-   R₁ and R₂ are each hydrogen; OH; trimethylsiloxy; C₁-C₆alkyl;    C₁-C₆alkoxy; or a radical of the formula

with the proviso that one of the radicals R₁ and R₂ is the bivalentradical of formula (2d);

-   R₃ is hydrogen; C₁-C₆alkyl; or C₁-C₆alkoxy;-   R₄ is hydrogen; or C₁-C₄alkyl; and-   R₅ and R₆, independently from each other are C₁-C₈alkyl;-   n is 0; or 1; and-   p is a number from 0 to 5.

The fluoren derivative (a₄) is preferably selected from derivatives ofcyano(9H-fluoren-9-ylidene)acetic acid, and diesters and polyesters of9H-fluoren-ylidene malonic acid. These compounds are disclosed in US2004/0057912.

Preferably, a 9-methylene-9H-fluoren derivative of formula

is used as component (a₄) in the present invention.

The naphthalene dicarboxylic acid derivatives (a₅) preferably correspondto the formula

wherein

-   R₁ is a radical of formula

-   k is a number from 1 to 13; and-   R₂ is selected from the group consisting of a compound of formula    (4a), or C₁-C₂₂alkyl.

The compounds are disclosed in WO 01/087528.

Preferably, compounds of the formula

are preferably used as component (a₅) in the present invention.

Dragosine, green tea concentrate and grape seed extract are typicalrepresentatives for stabilizers (a₆).

The phenolic antioxidants as listed in the Table below are usefulstabilizer components (a₇) in the present invention:

TABLE 1 com- pound of formula (AO-01)

(AO-02)

(AO-03)

(AO-04)

(AO-05)

(AO-06)

(AO-07)

(AO-08)

(AO-09)

(AO-10)

(AO-11)

(AO-12)

(AO-13)

(AO-14)

(AO-15)

(AO-16)

(AO-17)

(AO-18)

(AO-19)

(AO-20)

(AO-21)

(AO-22)

(AO-23)

(AO-24)

(AO-25)

(AO-26)

(AO-27)

Furthermore, the stabilizers disclosed in the following references, canadvantageously be used in the present composition: US 2004057914; WO2003039506; DE 10141473; WO 2003020317; WO 2003020224; US 2002197285; EP1127569; EP 1127568; FR 2801209; FR 2801207; “A new photostabilizer forfull spectrum sunscreens”, Cosmetics & Toiletries (2000), 115(6), p.37-45; U.S. Pat. No. 5,993,789.

The stabilizer compounds corresponding to components (a₁) to (a₇) areused as single components or can be used as mixtures in the presentcomposition consisting of two, three, four or even more of thecomponents (a₁) to (a₇).

The term “effective amount of a stabilizer” in accordance with thepresent invention is understood to mean an amount sufficient to producea noteworthy and significant improvement in the photostability of the UVfilter combination dibenzoylmethane derivative (b) and amino-substituted2-hydroxybenzophenone derivative (c). This minimum amount ofphotostabilizing agent to be employed, which can vary depending on thenature of the cosmetically acceptable vehicle used for the composition,can be determined without any difficulty by means of a conventional testfor measuring photostability.

Preferably, this UV filter is used in the cosmetic or dermatologicalcomposition in a concentration range from 1 to 10% b.w. of the cosmeticcomposition.

The 2-hydroxybenzophenone derivative according to component (c) of thecosmetic or dermatological composition preferably corresponds to formula

wherein

-   R₁ and R₂, independently from each other are hydrogen; C₁-C₃₀alkyl;    C₂-C₁₀alkenyl; C₃-C₁₀ cycloalkyl; or C₃-C₁₀cycloalkenyl; or-   R₁ and R₂ together form, with the nitrogen atom to which they are    bonded, a 5- or 6-membered heterocyclic ring member;-   R₃ and R₄, independently from each other, are each C₁-C₂₀alkyl;    C₂-C₁₀alkenyl; C₃-C₁₀cycloalkyl; C₃-C₁₀cycloalkenyl; C₁-C₁₂alkoxy;    (C₁-C₂₀)alkoxycarbonyl; C₁-C₁₂alkylamino; di(C₁-C₁₂)alkylamino; an    aryl or a heteroaryl radical which is optionally substituted; or a    water-solubilizing substituent selected from a carboxylate group, a    sulfonate group or an ammonium residue;-   X is hydrogen; —COOR₅; or —CONR₆R₇;-   R₅, R₆ and R₇, independently from each other, are hydrogen;    C₁-C₂₀alkyl; C₂-C₁₀alkenyl; C₃-C₁₀cycloalkyl; C₃-C₁₀cycloalkenyl,    —(Y′O)₀—Z′; or aryl;-   Y′ is —(CH₂)₂—; —(CH₂)₃—; —(CH₂)₄—; or —CH—(CH₃)—CH₂—;-   Z′ is —CH₂—CH₃; —CH₂—CH₂CH₃; —CH₂CH₂—CH₂—CH₃ or —CH(CH₃)—CH₃;-   n is an integer from 0 to 3; and-   o is an integer from 1 to 2.

C₁-C₂₀alkyl is for example methyl, ethyl, n-propyl, 1-methylethyl,n-butyl, 1-methylpropyl, 2-methylpropyl, 1,1-dimethyl-ethyl, n-pentyl,1-methylbutyl, 2-methylbutyl, 3-methyl-butyl, 2,2-dimethylpropyl,1-ethylpropyl, n-hexyl, 1,1-dimethylpropyl, 1,2-dimethylpropyl,1-methylpentyl, 2-methylpentyl, 3-methylpentyl, 4-methylpentyl,1,1-dimethylbutyl, 1,2-dimethylbutyl, 1,3-dimethylbutyl,2,2-dimethylbutyl, 2,3-dimethylbutyl, 3,3-dimethylbutyl, 1-ethylbutyl,2-ethylbutyl, 1,2,2-trimethylpropyl, 1-ethyl-1-methylpropyl,1-ethyl-2-methylpropyl, n-heptyl, n-octyl, n-nonyl, n-decyl, n-undecyl,n-dodecyl, n-tridecyl, n-tetradecyl, n-pentadecyl, n-hexadecyl,n-heptadecyl, n-octadecyl, n-nonadecyl or n-icosyl.

C₂-C₁₀alkenyl is for example: vinyl, n-propenyl, isopropenyl, 1-butenyl,2-butenyl, 1-pentenyl, 2-pentenyl, 2-methyl-1-butenyl,2-methyl-2-butenyl, 3-methyl-1-butenyl, 1-hexenyl, 2-hexenyl,1-heptenyl, 2-heptenyl, 1-octenyl or 2-octenyl.

C₁-C₁₂alkoxy is for example methoxy, ethoxy, n-propoxy, n-butoxy,n-pentoxy, 1-methylpropoxy, 3-methylbutoxy, 2,2-dimethylpropoxy,1-methyl-1-ethylpropoxy, octoxy, 2-methylpropoxy, 1,1-dimethylpropoxy,hexoxy, heptoxy or 2-ethylhexoxy.

C₃-C₁₀cycloalkyl is for example cyclopropyl, cyclobutyl, cyclopentyl,cyclohexyl, cycloheptyl, 1-methylcyclo-propyl, 1-ethylcyclopropyl,1-propylcyclopropyl, 1-butylcyclopropyl, 1-pentylcyclopropyl,1-methyl-1-butylcyclopropyl, 1,2-dimethylcyclopropyl,1-methyl-2-ethylcyclopropyl, cyclooctyl, cyclononyl or cyclodecyl.

C₃-C₁₀cycloalkenyl is for example cyclopropenyl, cyclobutenyl,cyclopentenyl, cyclopentadienyl, cyclohexenyl, 1,3-cyclohexadienyl,1,4-cyclohexadienyl, cycloheptenyl, cycloheptatrienyl, cyclooctenyl,1,5-cyclooctadienyl, cyclooctatetraenyl, cyclononenyl or cyclodecenyl.

The cycloalkyl or cycloalkenyl radicals can comprise one or moresubstituents (preferably from 1 to 3) and are selected, for example,from halogen, such as chlorine, fluorine or bromine; cyano; nitro;amino; C₁-C₄alkylamino; di(C₁-C₄)alkylamino; C₁-C₄alkyl; C₁-C₄alkoxy; orhydroxyl. They can also comprise from 1 to 3 heteroatoms, such assulphur, oxygen or nitrogen, the free valencies of which can be occupiedby a hydrogen or a C₁-C₄alkyl radical.

The aryl groups are preferably chosen from phenyl or naphthyl ringswhich can comprise one or more substituents (preferably from 1 to 3)chosen, for example, from halogen, such as chlorine, fluorine orbromine; cyano; nitro; amino; C₁-C₄alkylamino; di(C₁-C₄)alkylamino;C₁-C₄alkyl; C₁-C₄alkoxy; or hydroxyl.

Preference is more particularly given to phenyl, methoxyphenyl andnaphthyl.

The heteroaryl groups generally comprise one or more heteroatoms chosenfrom sulphur, oxygen or nitrogen.

The water-solubilizing groups are, for example, carboxylate orsulphonate groups and more particularly their salts with physiologicallyacceptable cations, such as alkali metal salts or trialkylammoniumsalts, such as tri(hydroxyalkyl)-ammonium or2-methylpropan-1-ol-2-ammonium salts. Mention may also be made ofammonium groups, such as alkylammoniums, and their salified forms withphysiologically acceptable anions.

Mention may in particular be made, as examples of the 5- or 6-memberedheterocyclic ring member; formed by the R₁ and R₂ with the nitrogenatom, of pyrrolidine or piperidine.

The amino groups can be attached to the benzene ring in the ortho, metaor para position with respect to the carbonyl radical and morepreferably in the para position.

Preferably, the 2-hydroxybenzophenone derivative (b) in the cosmetic ordermatological composition corresponds to formula

wherein

-   R₁ and R₂, independently from each other, are hydrogen; or    C₁-C₃alkyl; or together form, with the nitrogen atom to which they    are bonded, a 5- or 6-membered heterocyclic ring member; and-   R₅ is hydrogen; C₁-C₅alkyl; or a C₃-C₆cycloalkyl.

Most preferably the compound of formula

is used as component (b) in the cosmetic or dermatological composition.

The dibenzoylmethane derivatives according to component (b) according tothe present invention are products which are already well known per seand which are disclosed in particular in FR 2,326,405, FR 2,440,933 andEP 0,114,607, the teachings of which documents are, insofar as theyaffect the actual definition of these products, entirely included by wayof references in the present description.

According to the present invention, it is possible, of course, to employone or more dibenzoylmethane derivatives.

Examples of dibenzoylmethane derivatives (b) are:2-methyldibenzoylmethane; 4-methyldibenzoylmethane;4-isopropyldibenzoylmethane; 4-tert-butyldibenzoylmethane;2,4-dimethyldibenzoylmethane; 2,5-dimethyldibenzoylmethane;4,4′-diisopropyldibenzoylmethane; 4,4′-dimethoxydibenzoylmethane;4-tert-butyl-4′-methoxydibenzoylmethane;2-methyl-5-isopropyl-4′-methoxydibenzoyl methane;2-methyl-5-tert-butyl-4′-methoxydibenzoylmethane;2,4-dimethyl-4′-methoxydibenzoylmethane; or2,6-dimethyl-4-tert-butyl-4′-methoxydibenzoylmethane.

Preference is very particularly given according to the presentinvention, among the above-mentioned dibenzoylmethane derivatives, tothe use of 4-tert-butyl-4′-methoxydibenzoylmethane, in particular thatoffered for sale under the trademark of “Parsol 1789” byHoffmann-LaRoche, this screening agent corresponding to the followingformula

Another preferred dibenzoylmethane derivative according to the presentinvention is 4-isopropyldibenzoylmethane, a screening agent sold underthe name of “Eusolex 8020” by Merck and corresponding to the formula

or 4-Ethylhexyl-4′Methoxydibenzoylmethane corresponding to formula

The dibenzoylmethane derivative (b) isresent in the compositions inaccordance with the invention at contents preferably ranging from 0.3 to10% by weight and more preferably from 0.5 to n10% by weight and moreparticularly from 0.5 to 8% by weight, with respect to the total weightof the composition.

The cosmetic or dermatological composition comprising at least

-   1 to 10% b.w of a stabilizing agent (a) selected from a    diphenylacrylate UV filter (a₁), a benzylidene cmphor derivative    (a₂), an organosiloxane comprising benzalemalonate groups (a₃), a    fluoren derivative (a₄), and a naphthalene dicarboxylic acid    derivative (a₅);-   2.0 to 5% b.w of a dibenzoylmethane derivative (b); and-   0.3 to 10% b.w. of an amino-substituted 2-hydroxybenzophenone    derivative (c);-   is a further object of the present invention.

The cosmetic or dermatological compositions according to the presentinvention comprising components (a), (b) and (c) are particularlysuitable as UV filters, i.e. for protecting UV-sensitive organicmaterials, in particular the skin and hair of humans and animals, fromthe harmful effects of UV radiation. These compositions are thereforesuitable as sunscreens in cosmetic, pharmaceutical and veterinarymedical preparations.

The cosmetic formulations or dermatological compositions according tothe present invention may additionally contain one or more than onefurther UV filter as listed in Table 1.

TABLE 2 Suitable UV filter substances and adjuvants which can beadditionally used with the UV absorbers according to the presentinvention No. Chemical Name CAS No. 1(+/−)-1,7,7-trimethyl-3-[(4-methylphenyl)methylene]  36861-47-9bicyclo[2.2.1]-heptan-2-one; p-methyl benzylidene camphor 21,7,7-trimethyl-3-(phenylmethylene)bicyclo[2.2.1]  15087-24-8heptan-2-one; benzylidene camphor 3(2-Hydroxy-4-methoxyphenyl)(4-methylphenyl)  1641-17-4 methanone 42,4-dihydroxybenzophenone   131-56-6 52,2′,4,4′-tetrahydroxybenzophenone   131-55-5 6 2-Hydroxy-4-methoxybenzophenone   131-57-7 7 2-Hydroxy-4-methoxy benzophenone-5-sulfonicacid  4065-45-6 8 2,2′-dihydroxy-4,4′-dimethoxybenzophenone   131-54-4 92,2′-Dihydroxy-4-methoxybenzophenone   131-53-3 10Alpha-(2-oxoborn-3-ylidene)toluene-4-sulphonic acid  56039-58-8 and itssalts; Mexoryl SL 11 1-[4-(1,1-dimethylethyl)phenyl]-3-(4-methoxyphenyl) 70356-09-1 propane-1,3-dione; avobenzone 12 MethylN,N,N-trimethyl-4-[(4,7,7-trimethyl-3-  52793-97-2oxobicyclo[2,2,1]hept-2-ylidene)methyl]anilinium sulphate; Mexoryl SO 223,3,5-Trimethyl cyclohexyl-2-hydroxy benzoate;   118-56-9 homosalate 23Isopentyl p-methoxycinnamate; isoamyl methoxy  71617-10-2 cinnamate 27Menthyl-o-aminobenzoate   134-09-8 28 Menthyl salicylate   89-46-3 292-Ethylhexyl 2-cyano, 3,3-diphenylacrylate;  6197-30-4 Octocrylene 302-ethylhexyl 4-(dimethylamino)benzoate  21245-02-3 31 2-ethylhexyl4-methoxycinnamate; octyl methoxy  5466-77-3 cinnamate 32 2-ethylhexylsalicylate   118-60-5 33 Benzoic acid,4,4′,4″-(1,3,5-triazine-2,4,6-triyltriimino)  88122-99-0 tris-,tris(2-ethylhexyl)ester; 2,4,6-Trianilino-(p-carbo-2′-ethylhexyl-1′-oxi)-1,3,5-triazine; octyl triazone 34 4-aminobenzoicacid   150-13-0 35 Benzoic acid, 4-amino-, ethyl ester, polymer with113010-52-9 oxirane 38 2-phenyl-1H-benzimidazole-5-sulphonic acid;phenyl-  27503-81-7 benzimidazolsulfonic acid 39 2-Propenamide,N-[[4-[(4,7,7-trimethyl-3-oxobicyclo 147897-12-9[2.2.1]hept-2-ylidene)methyl]phenyl]methyl]-, homopolymer 40Triethanolamine salicylate  2174-16-5 413,3′-(1,4-phenylenedimethylene)bis[7,7-dimethyl-2-  90457-82-2oxo-bicyclo[2.2.1]heptane-1 methanesulfonic acid]; Cibafast H 42Titanium dioxide  13463-67-7 44 Zinc oxide  1314-13-2 452,2′-Methylene-bis-[6-(2H-benzotriazol-2-yl)-4- 103597-45-1(1,1,3,3-tetramethyl-butyl)-phenol]; Tinosorb M 462,4-bis{[4-(2-ethylhexyloxy)-2-hydroxy]-phenyl}-6-(4- 187393-00-6methoxy-phenyl)-(1,3,5)-triazine; Tinosorb S 471H-Benzimidazole-4,6-disulfonic acid, 2,2′-(1,4- 180898-37-7phenylene)bis-, disodium salt 48 Benzoic acid,4,4′-[[6-[[4-[[(1,1-dimethylethyl)amino] 154702-15-5carbonyl]phenyl]-amino]1,3,5-triazine-2,4-diyl] diimino]bis-,bis(2-ethylhexyl)ester; diethylhexyl butamido triazone; Uvasorb HEB 49Phenol, 2-(2H-benzotriazol-2-yl)-4-methyl-6-[2- 155633-54-8methyl-3-[1,3,3,3-tetramethyl-1-[(trimethylsilyl)oxy]disiloxanyl]propyl]-; drometrizole trisiloxane; Mexoryl XL 50Dimethicodiethylbenzalmalonate; Polysilicone 15; 207574-74-1 Parsol SLX51 Benzenesulfonic acid, 3-(2H-benzotriazol-2-yl)-4-  92484-48-5hydroxy-5-(1-methylpropyl)-, monosodium salt; Tinogard HS 52 Benzoicacid, 2-[4-(diethylamino)-2-hydroxybenzoyl]-, 302776-68-7 hexyl ester;Uvinul a plus 53 1-Dodecanaminium, N-[3-[[4-(dimethylamino)benzoyl]156679-41-3 amino]propyl]-N,N-dimethyl-, salt with 4-methyl-benzenesulfonic acid (1:1); Escalol HP610 54 1-Propanaminium,N,N,N-trimethyl-3-[(1-oxo-3- 177190-98-6 phenyl-2-propenyl)-amino]-,chloride 55 1H-Benzimidazole-4,6-disulfonic acid, 2,2′-(1,4- 170864-82-1phenylene)bis- 56 1,3,5-Triazine, 2,4,6-tris(4-methoxyphenyl)- 7753-12-0 57 1,3,5-Triazine, 2,4,6-tris[4-[(2-ethylhexyl)oxy]phenyl]-208114-14-1 58 1-Propanaminium, 3-[[3-[3-(2H-benzotriazol-2-yl)-5-340964-15-0 (1,1-dimethylethyl)-4-hydroxyphenyl]-1-oxopropyl]amino]-N,N-diethyl-N-methyl-, methyl sulfate (salt) 59 2-Propenoic acid,3-(1H-imidazol-4-yl)-   104-98-3 60 Benzoic acid, 2-hydroxy-,[4-(1-methylethyl)phenyl]  94134-93-7 methyl ester 611,2,3-Propanetriol, 1-(4-aminobenzoate); glyceryl   136-44-7 PABA 62Benzeneacetic acid, 3,4-dimethoxy-a-oxo-  4732-70-1 63 2-Propenoic acid,2-cyano-3,3-diphenyl-, ethyl ester  5232-99-5 64 Anthralinic acid,p-menth-3-yl ester   134-09-8 652,2′-bis(1,4-phenylene)-1H-benzimidazole-4,6- 349580-12-7, disulphonicacid mono sodium salt or Disodium phenyl dibenzimidazole tetrasulfonateor Neoheliopan AP 66 1,3,5-Triazine-2,4,6-triamine, N,N′-bis[4-[5-(1,1-288254-16-0 dimethylpropyl)-2-benzoxazolyl]phenyl]-N″-(2- ethylhexyl)-or Uvasorb K2A 67 Merocyanine derivatives as described in WO 2004006878and in IPCOM000022279D 68

68 sterols (cholesterol, lanosterol, phytosterols), as described inWO0341675 69 mycosporines and/or mycosporine-like amino acids asdescribed in WO2002039974, e.g. Helioguard 365 from Milbelle AG,isolated mycosporine like amino acids from the red alga porphyraumbilicalis (INCI: Porphyra Umbilicalis) that are encapsulated intoliposomes,) 70 alpha-lipoic-acid as described in DE 10229995 71synthetic organic polymers as described in EP 1371358, [0033]-[0041] 72phyllosilicates as described in EP 1371357 [0034]- [0037] 73 silicacompounds as described in EP1371356, [0033]- [0041] 74 inorganicparticles as described in DE10138496 [0043]- [0055] 75 latex particlesas described in DE10138496 [0027]- [0040] 761H-Benzimidazole-4,6-disulfonic acid, 2,2′-(1,4- 180898-37-7phenylene)bis-, disodium salt; Bisimidazylate; Neo Heliopan APC

The cosmetic or dermatological preparations can be prepared byphysically mixing the UV absorber(s) with the adjuvant using customarymethods, for example by simply stirring together the individualcomponents, especially by making use of the dissolution properties ofalready known cosmetic UV absorbers, like octyl methoxy cinnamate,salicylic acid isooctyl ester etc.

The stabilizing agents (a₁)-(a₇) can also be used for stabilizing thespecific amino-substituted 2-hydroxybenzophenone derivative (c). This isanother object of the present invention.

Cosmetic or pharmaceutical preparations contain from 0.05-40% by weight,based on the total weight of the composition, of the UV filtercomponents (a), (b) and (c).

Preference is given to the use of mixing ratios of the UV filtercomponents (a), (b) and (c) according to the present invention andoptionally further light-protective agents (as described in Table 2)from 1:99 to 99:1, preferably from 1:95 to 95:1 and most preferably from10:90 to 90:10, based on weight. Of special interest are mixing ratiosof from 20:80 to 80:20, preferably from 40:60 to 60:40 and mostpreferably approximately 50:50. Such mixtures can be used, inter alia,to improve the solubility or to increase the UV absorption.

The UV filter compounds (a), (b) and (c) according to the presentinvention as well as the additional filters listed in Table 1 can beused either in the dissolved state (soluble organic filters, solubilizedorganic filters) or in the micronised state (nanoscalar organic filters,particulate organic filters, UV-absorber pigments).

Any known process suitable for the preparation of microparticles can beused for the preparation of the micronised UV absorbers, for examplewet-milling, wet-kneading, spray-drying from a suitable solvent, by theexpansion according to the RESS process (Rapid Expansion ofSupercritical Solutions) of supercritical fluids (e.g. CO₂) in which theUV filter or filters is/are dissolved, by reprecipitation from suitablesolvents, including supercritical fluids (GASR process=Gas Anti-SolventRecrystallisation/PCA process=Precipitation with CompressedAnti-solvents).

As milling apparatus for the preparation of the micronised organic UVabsorbers there may be used, for example, a jet mill, ball mill,vibratory mill or hammer mill, preferably a high-speed mixing mill. Thegrinding is preferably carried out with a grinding aid. As kneadingapparatus for the preparation of the micronised organic UV absorbersexamples are typically sigma-hook batch kneaders but also serial batchkneaders (IKA-Werke) or continuous kneaders (Contiuna from Werner andPfleiderer).

Useful low molecular weight grinding aids for the micronizing processesmentioned above are surfactants and emulsifies.

Useful polymeric grinding aids for water dispersion are cosmeticallyacceptable water soluble polymers with Mn>500 g/mol, for exampleacrylates (Salcare types), modified or non-modified polysaccharides,polyglucosides or xanthan gum. Furthermore an alkylated vinylpyrrolidonepolymer, a vinylpyrrolidone/vinyl acetate copolymer, an acyl glutamate,an alkyl polyglucoside, ceteareth-25 or a phospholipid may be used. Oildispersions may contain cosmetically acceptable waxy polymers or naturalwaxes as polymeric grinding aid in order to adjust viscosity during andafter processing. Examples of other useful polymeric grinding aids aredisclosed below in the chapter “polymers”.

Useful solvents for the grinding process are water, brine,(poly-)ethylenglycol, glycerine or cosmetically acceptable oils. Otheruseful solvents are disclosed below in the chapters “esters of fattyacids”, “natural and synthetic triglycerides including glyceryl estersand derivatives”, “perlescent waxes”, “hydrocarbon oils” and “siliconesor siloxanes”.

The micronised UV absorbers so obtained usually have an average particlesize from 0.02 to 2, preferably from 0.03 to 1.5, and more especiallyfrom 0.05 to 1.0 micrometer.

The UV absorbers used in the cosmetic or dermatological compositions ofthe present invention can also be used as dry substrates in powder form.For that purpose the UV absorbers are subjected to known grindingmethods, such as vacuum atomization, countercurrent spray-drying etc.

The UV absorbers used in the cosmetic or dermatological compositions ofthe present invention can also be used in specific carriers forcosmetics, for example in solid lipid nanoparticles (SLN) or in inertsol-gel microcapsules wherein the UV absorbers are encapsulated(Pharmazie, 2001 (56), p. 783-786).

The cosmetic or dermatological preparations may be, for example, creams,gels, lotions, alcoholic and aqueous/alcoholic solutions, emulsions,wax/fat compositions, stick preparations, powders or ointments. Inaddition to the above-mentioned UV filters, the cosmetic orpharmaceutical preparations may contain further adjuvants as describedbelow.

As water- and oil-containing emulsions (e.g. W/O, O/W, O/W/O and W/O/Wemulsions or microemulsions) the preparations contain, for example, from0.1 to 30% by weight, preferably from 0.1 to 15% by weight andespecially from 0.5 to 10% by weight, based on the total weight of thecomposition, of a UV absorber composition comprising the components (a),(b) and (c), from 1 to 60% by weight, especially from 5 to 50% by weightand preferably from 10 to 35% by weight, based on the total weight ofthe composition, of at least one oil component, from 0 to 30% by weight,especially from 1 to 30% by weight and preferably from 4 to 20% byweight, based on the total weight of the composition, of at least oneemulsifier, from 10 to 90% by weight, especially from 30 to 90% byweight, based on the total weight of the composition, of water, and from0 to 88.9% by weight, especially from 1 to 50% by weight, of furthercosmetically acceptable adjuvants.

The cosmetic or dermatological preparations may be, for example, creams,gels, lotions, alcoholic and aqueous/alcoholic solutions, emulsions,wax/fat compositions, stick preparations, powders or ointments. Inaddition to the above mentioned UV filters, the cosmetic orpharmaceutical preparations may contain further adjuvants as describedbelow.

As water- and oil-containing emulsions (e.g. W/O, O/W, O/W/O and W/O/Wemulsions or microemulsions) the preparations contain, for example, from0.1 to 30% by weight, preferably from 0.1 to 15% by weight andespecially from 0.5 to 10% by weight, based on the total weight of thecomposition, of one or more UV absorbers, from 1 to 60% by weight,especially from 5 to 50% by weight and preferably from 10 to 35% byweight, based on the total weight of the composition, of at least oneoil component, from 0 to 30% by weight, especially from 1 to 30% byweight and preferably from 4 to 20% by weight, based on the total weightof the composition, of at least one emulsifier, from 10 to 90% byweight, especially from 30 to 90% by weight, based on the total weightof the composition, of water, and from 0 to 88.9% by weight, especiallyfrom 1 to 50% by weight, of further cosmetically acceptable adjuvants.

The cosmetic or pharmaceutical compositions/preparations according tothe invention may also contain one or one more additional compounds likefatty alcohols, natural or synthetic triglycerides including glycerylesters and derivatives, pearlescent waxes, hydrocarbon oils, siliconesor siloxanes (organosubstituted polysiloxanes), fluorinated orperfluorinated oils, mulsifiers, super-fatting agents, surfactants,consistency regulators/thickeners and rheology modifiers, polymers,biogenic active ingredients, deodorising active ingredients,anti-dandruff agents, antioxidants, hydrotropic agents, preservativesand bacteria-inhibiting agents, perfume oils, colourants, and polymericbeads or hollow spheres as SPF enhancers.

Cosmetic or pharmaceutical formulations are contained in a wide varietyof cosmetic preparations. There come into consideration, for example,especially the following preparations:

-   -   skin-care preparations, e.g. skin-washing and cleansing        preparations in the form of tablet-form or liquid soaps,        soapless detergents or washing pastes,    -   bath preparations, e.g. liquid (foam baths, milks, shower        preparations) or solid bath preparations, e.g. bath cubes and        bath salts;    -   skin-care preparations, e.g. skin emulsions, multi-emulsions or        skin oils;    -   cosmetic personal care preparations, e.g. facial make-up in the        form of day creams or powder creams, face powder (loose or        pressed), rouge or cream make-up, eye-care preparations, e.g.        eyeshadow preparations, mascara, eyeliner, eye creams or eye-fix        creams; lip-care preparations, e.g. lipsticks, lip gloss, lip        contour pencils, nail-care preparations, such as nail varnish,        nail varnish removers, nail hardeners or cuticle removers;    -   foot-care preparations, e.g. foot baths, foot powders, foot        creams or foot balsams, special deodorants and antiperspirants        or callus-removing preparations;    -   light-protective preparations, such as sun milks, lotions,        creams or oils, sunblocks or tropicals, pre-tanning preparations        or after-sun preparations;    -   skin-tanning preparations, e.g. self-tanning creams;    -   depigmenting preparations, e.g. preparations for bleaching the        skin or skin-lightening preparations;    -   insect-repellents, e.g. insect-repellent oils, lotions, sprays        or sticks;    -   deodorants, such as deodorant sprays, pump-action sprays,        deodorant gels, sticks or roll-ons;    -   antiperspirants, e.g. antiperspirant sticks, creams or roll-ons;    -   preparations for cleansing and caring for blemished skin, e.g.        synthetic detergents (solid or liquid), peeling or scrub        preparations or peeling masks;    -   hair-removal preparations in chemical form (depilation), e.g.        hair-removing powders, liquid hair-removing preparations, cream-        or paste-form hair-removing preparations, hair-removing        preparations in gel form or aerosol foams;    -   shaving preparations, e.g. shaving soap, foaming shaving creams,        non-foaming shaving creams, foams and gels, preshave        preparations for dry shaving, aftershaves or aftershave lotions;    -   fragrance preparations, e.g. fragrances (eau de Cologne, eau de        toilette, eau de parfum, parfum de toilette, perfume), perfume        oils or perfume creams;    -   cosmetic hair-treatment preparations, e.g. hair-washing        preparations in the form of shampoos and conditioners, hair-care        preparations, e.g. pretreatment preparations, hair tonics,        styling creams, styling gels, pomades, hair rinses, treatment        packs, intensive hair treatments, hair-structuring preparations,        e.g. hair-waving preparations for permanent waves (hot wave,        mild wave, cold wave), hair-straightening preparations, liquid        hair-setting preparations, hair foams, hairsprays, bleaching        preparations, e.g. hydrogen peroxide solutions, lightening        shampoos, bleaching creams, bleaching powders, bleaching pastes        or oils, temporary, semi-permanent or permanent hair colourants,        preparations containing self-oxidising dyes, or natural hair        colourants, such as henna or camomile.

The final formulations listed may exist in a wide variety ofpresentation forms, for example:

-   -   in the form of liquid preparations as a W/O, O/W, O/W/O, W/O/W        or PIT emulsion and all kinds of microemulsions,    -   in the form of a gel,    -   in the form of an oil, a cream, milk or lotion,    -   in the form of a powder, a lacquer, a tablet or make-up,    -   in the form of a stick,    -   in the form of a spray (spray with propellent gas or pump-action        spray) or an aerosol,    -   in the form of a foam, or    -   in the form of a paste.

Of special importance as cosmetic preparations for the skin arelight-protective preparations, such as sun milks, lotions, creams, oils,sunblocks or tropicals, pretanning preparations or after-sunpreparations, also skin-tanning preparations, for example self-tanningcreams. Of particular interest are sun protection creams, sun protectionlotions, sun protection milk and sun protection preparations in the formof a spray.

Of special importance as cosmetic preparations for the hair are theabove-mentioned preparations for hair treatment, especially hair-washingpreparations in the form of shampoos, hair conditioners, hair-carepreparations, e.g. pretreatment preparations, hair tonics, stylingcreams, styling gels, pomades, hair rinses, treatment packs, intensivehair treatments, hair-straightening preparations, liquid hair-settingpreparations, hair foams and hairsprays. Of special interest arehair-washing preparations in the form of shampoos.

A shampoo has, for example, the following composition: from 0.01 to 5%by weight of a UV absorber composition according to the inventioncomprising the components (a), (b) and (c), 12.0% by weight of sodiumlaureth-2-sulfate, 4.0% by weight of cocamidopropyl betaine, 3.0% byweight of sodium chloride, and water ad 100%.

Examples of Cosmetic and Pharmaceutical Preparations (X=PreferredCombinations)

O/W systems: Ingredients 1 2 3 4 5 6 7 8 Emulsifiers Potassium CetylPhosphate 2-5% X Cetearyl Alcohol/Dicetyl X Phosphate/Ceteth-10Phosphate 2-6% Sodium Stearyl Phtalamate 1-2% X CetearylAlcohol/Behentrimonium X Methosulfate 1-5% Quaternium-32 1-5% XDimethicone copolyol/Caprylic/ X Capric Triglyceride (1-4%)Steareth-2/Steareth-21 2-5% X Polyglyceryl Methyl Glucose X Distearate1-4% Lipophilic emollient/dispersant X X X X X X X X oil 15-20% FattyAlcohols and/or Waxes 1-5% X X X X X X X X Thickeners (water swellable XX X X X X X X thickeners) 0.5-1.5% Preservatives 0.5-1% X X X X X X X XChelating agents (such as X X X X X X X X EDTA) 0-0.2% Antioxidants0.05-0.2% X X X X X X X X Water deionized Qs 100% X X X X X X X XPerfume oils 0.1-0.4% X X X X X X X X UV-absorber composition X X X X XX X X comprising components (a), (b) and (c) according to the invention;0.1-20% UV-absorber as described in X X X X X X X X Table 2; 0-30%

W/O systems Ingredients 1 2 3 4 5 Emulsifiers X X X X X Polyglyceryl-2Dipolyhydroxystearate 2-4% X X X X X PEG-30 Dipolyhydroxystearate 2-4% XRapeseed Oil Sorbitol Esters 1-5% X PEG-45/Dodecyl Glycol Copolymer 1-5%X Sorbitan Oleate/Polycerol-3 ricinoleate 1-5% X Lipophilicemollient/dispersant oil 10-20% X X X X X Fatty Alcohols and/or Waxes10-15% X X X X X Electrolytes (NaCl, MgSO₄) 0.5-1% X X X X X Polyolphase (Propylene glycol, glycerin) 1-8% X X X X X Preservatives 0.3-0.8%X X X X X Perfume oils 0.1-0.4% X X X X X Chelating agents (such asEDTA) 0-0.2% X X X X X Antioxidants 0.05-0.2% X X X X X Water deionizedQs 100% X X X X X UV-absorber composition comprising X X X X Xcomponents (a), (b) and (c) according to the invention; 0.1-20%UV-absorber as described in Table 2; 0-30% X X X X X

W/Silicone systems Ingredients 1 2 3 4 DimethiconeCopolyol/Cyclomethicone 5-10% X X Laurylmethicone Copolyol 5-10% X XCyclopentasiloxane 15-25% X X Dimethicone 15-25% X XDimethicone/Vinyldimethicone Crosspolymer 1-10% X X X XHumectant/polyols (Propylene glycol, glycerin . . . ) X X X X 2-8%Chelating agents (such as EDTA) 0-0.2% X X X X Antioxidants 0.05-0.2% XX X X Preservatives 0.3-0.8% X X X X Perfume oils 0.1-0.4% X X X X Waterdeionized Qs 100% X X X X UV-absorber composition comprising componentsX X X X (a), (b) and (c) according to the invention; 0.1-20% UV-absorberas described in Table 2; 0-30% X X X X

Multiple emulsions Ingredients 1 2 3 4 5 6 7 8 9 10 11 12 PEG-30Dipolyhydroxystearate (2-6%) X X X Cetyl Dimethicone Copolyol 1-3% X XPEG-30 Dipolyhydroxystearate/ X X Steareth-2/Steareth-21 4-6%Polyglyceryl-2 Dipolyhydroxy- X X stearate 1-3% Polyglyceryl-6Ricinoleate 1-3% X X X Oil phase 15-30% Fatty acid esters X X X X X X XNatural and synthetic Triglycerides X X X X X X X Hydrocarbon oils X X XX X X X Silicone oils X X X X X X X Preservatives 0.3-0.8% X X X X X X XX X X X X Water Deioniz. qs 100% X X X X X X X X X X X X SorbitanStearate/Sucrose Cocoate X X X 3-7% Sucrose Laurate 3-7% X X X Poloxamer407 3-7% X X X Polyoxyethylene(20)Sorbate X X X Monoleate 3-5% Primaryemulsion W1/O 50% X X X X X X X X X X X X Thickeners (water swellable XX X X X X X X X X X X polymers) 0.3-1% Water deionized Qs 100% X X X X XX X X X X X X Perfume oils 0.1-0.4% X X X X X X X X X X X X UV-absorbercomposition comprising X X X X X X X X X X X X components (a), (b) and(c) according to the invention; 0.1-20% UV-absorber as described inTable X X X X X X X X X X X X 2; 0-30%

O1/W/O2 emulsions Ingredients 1 2 3 4 5 6 7 8 Primary emulsion O1/WPEG-60 Hydrogenated Castor X X X X Oil 25% Steareth-25 25% X X X X Oilphase 75% Fatty acid esters X X Natural and synthetic Triglycerides X XHydrocarbon oils X X Silicone oils X X Preservatives 0.3-0.8% X X X X XX X X Water deionized Qs 100% X X X X X X X X Nonionic multifunctional XX X X X X X X W/O emulsifier 2-5% Waxes 1-5% X X X X X X X X Oil phase20-30% X X X X X X X X Silicone oils Primary emulsion O1/W 15% X X X X XX X X Electrolytes (NaCl, MgSO₄) X X X X X X X X 0.1-0.5% Waterdeionized Qs 100% X X X X X X X X Perfume oils 0.1-0.4% X X X X X X X XUV-absorber composition X X X X X X X X comprising components (a), (b)and (c) according to the invention; 0.1-20% UV-absorber as described inX X X X X X X X Table 2; 0-30%

Microemulsions Ingredients 1 2 3 4 5 6 7 8 9 10 PEG-8 Caprylic/Capric XX X X X Glycerides 10-25% PPG-5-ceteth-20 10-25% X X X X XPolyglyceryl-6 X X Isostearate 5-15% Polyglyceryl-3 X X Diisostearate5-15% Polyglyceryl-6 X X Dioleate 5-15% PPG-10 Cetyl Ether X X 5-15%Ethoxydiglycol 5-15% X X Oil phase 10-80% X X X X X X X X X X IsostearylBenzoate X X X X X X X X X X Isostearyl Isostearate X X X X X X X X X XPEG-7 Glyceryl Cocoate X X X X X X X X X X Cyclomethicone X X X X X X XX X X Polyalcohols/ X X X X X X X X X X Humectants 1-10% Preservatives0.3-0.8% X X X X X X X X X X Perfume oils 0.1-0.4% X X X X X X X X X XWater Deioniz. qs 100% X X X X X X X X X X UV-absorber X X X X X X X X XX composition comprising components (a), (b) and (c) according to theinvention; 0.1-20% UV-absorber as X X X X X X X X X X described in Table2; 0-30%

O/W Spray emulsions Ingredients 1 2 3 4 5 6 Alkyl Phosphates 0.1-5% X XX Glucosidic derivatives 0.1-5% X X X Solubilisants Ethoxylated Glycerylethers 0.1-1% X X Polysorbates 0.1-1% X X Ethoxylated Oleyl ethers0.1-1% X X PVP/VA Coplymer 1-10% X X X PVM/MA Copolymer 1-10% X X X Oilphase 5-20% X X X X X X Natural oils (Meadowfoam, X X X X X X Jojoba,Macadamia . . . ) Fatty acids esters X X X X X X Mineral oils X X X X XX Silicone oils X X X X X X Alcohol 0-50% X X X X X X Thickeners0.1-0.5% X X X X X X Polyacrylates X X X X X X Aluminium/MagnesiumSilicates X X X X X X Gums X X X X X X Neutralizing agents 0-1% X X X XX X Polyalcohols/Humectants 1-5% X X X X X X Chelating agents (such asEDTA) 0-0.2% X X X X X X Antioxidants 0.05-0.2% X X X X X X WaterDeioniz. qs 100% X X X X X X Perfume oils 0.1-0.5% X X X X X XPreservatives 0.4-1% X X X X X X UV-absorber composition comprising X XX X X X components (a), (b) and (c) according to the invention; 0.1-20%UV-absorber as described in Table 2; 0-30% X X X X X X

G - Aqueous Ingredients 1 2 3 4 5 6 7 8 9 10 11 12 Thickeners NaturalThickener 1-5% X X X X Semi-synthetic Thickener 1-5% X X X X SyntheticThickener 0.3-1.3% X X X X Neutralizing Agents 0.5-1.5% X X X X X X X XX X X X Polyols - Humectants 5-50% X X X X X X X X X X X XPolyquaternium series 1-5% X X X X X X PVM/MA Copolymer 1-5% X X X X X XPreservatives 0.5-1% X X X X X X X X X X X X Chelating Agents (as EDTA)<0.1% X X X X X X X X X X X X Water Deioniz. qs 100% X X X X X X X X X XX X Perfume oils 0.05-0.4% X X X X X X X X X X X X Ethoxylated Glycerylethers 0.1-5% X X X Polysorbates 0.1-5% X X X Ethoxylated Oleyl ethers0.1-5% X X X X X X UV-absorber composition comprising X X X X X X X X XX X X components (a), (b) and (c) according to the invention; 0.1-20%UV-absorber as described in Table X X X X X X X X X X X X 2; 0-30%

Oleogels Ingredients 1 2 3 4 5 6 7 8 9 10 Hydrogenated X X Lecithin1-10% Silica Dimethyl X X Silylate 1-10% Silica 1-5% X X C₂₄₋₂₈ Alkyl XX Dimethicone 1-5% Aluminium or X X Magnesium Stearate 1-5% Polyols -Humectants X X X X X X X X X X 5-70% Oil phase 20-90% Dicaprylyl Ether XX X Phenyl Trimethicone X X Hydrogenated X Polyisobutene IsopropylIsostearate X X Oleogel basis (Mineral X X oil and hydrogenatedButylene/Ethylene or Ethylene/Propylene Styrene Copolymer) Silicone wax1-10% X X X X X X X X X X Dimethiconol Behenate X X X X X X X X X XDimethiconol Stearate X X X X X X X X X X Perfume oils 0.1-0.5% X X X XX X X X X X Antioxidants 0.05-0.2% X X X X X X X X X X UV-absorber X X XX X X X X X X composition comprising components (a), (b) and (c)according to the invention; 0.1-20% UV-absorber as X X X X X X X X X Xdescribed in Table 2; 0-30%

Light/dry cosmetic oils Ingredients 1 2 3 4 Hydrocarbon oils 30-70% X XFatty acid esters branched or not 10-50% X X Silicones/Siloxanes 0-10% XX Perfluorinated oils and Perfluoroethers 0-10% X X Viscosifying agents0-10% X X X X Esters of long chain acids and alcohols 0-2% X X X XAntioxidants 0.1-1% X X X X Solubilisants/dispersing agents 0-5% X X X XPerfume oils 0.1-0.5% X X X X UV-absorber composition comprisingcomponents X X X X (a), (b) and (c) according to the invention; 0.1-20%UV-absorber as described in Table 2; 0-30% X X X X

Foaming/mousse products Ingredients 1 SD Alcohol 40 0-8% X Propellant8-15% X Nonionic Emulsifier/Surfactant 0.5-3% X Corrosion Inhibitor 0-1%X Perfume oils 0.1-0.5% X Preservatives 0.1-1% X Miscellaneous 0-1% XUV-absorber composition comprising components X (a), (b) and (c)according to the invention; 0.1-20% UV-absorber as described in Table 2;0-30% X

Stick products Ingredients 1 Waxes 15-30% X Natural and silicone oils20-75% X Lanoline derivatives 5->50% X Esters of lanolin x Acetylatedlanolin x Lanolin oil x Colorants and pigments 10-15% X Antioxidants0.1-0.8% X Perfume oils 0.1-2% X Preservatives 0.1-0.7% X UV-absorbercomposition comprising components X (a), (b) and (c) according to theinvention; 0.1-20% UV-absorber as described in Table 2; 0-30% X

Liquid and compact Ingredients 1 2 Liquid foundation Powder phase 10-15%X Oil phase 30%-40%; 75% (only for anhydrous form) XThickener/suspending agents1-5% X Film forming polymers 1-2% XAntioxidants 0.1-1% X Perfume oils 0.1-0.5% X Preservatives 0.1-0.8% XWater deionized Qs 100% X Compact powder Powder phase 15-50% X Oil phase15-50% X Polyol phase 5-15% X Antioxidants 0.1-1% X Perfume oils0.1-0.5% X Preservatives 0.1-0.8% X For the two product formsUV-absorber composition comprising components X X (a), (b) and (c)according to the invention; 0.1-20% UV-absorber as described in Table 2;0-30% X X

Conditioning Shampoos Ingredients 1 Primary surfactants (listedpreviously) 5-10% X Secondary surfactants (listed previously) 5-15% XFoam Stabilizers (listed previously) 0-5% X Water deionized 40-70% XActives 0-10% X Conditioners x Refatting agents x Moisturizing agents xThickeners/Rheology mofifiers 0-3% X Humectants 0-2% X PH adjustingagents 0-1% X Preservatives 0.05-1% X Perfume oils 0.1-1% X Antioxidants0.05-0.20% X Chelating Agents (EDTA) 0-0.2% X Opascifying agents 0-2% XUV-absorber composition comprising components X (a), (b) and (c)according to the invention; 0.1-20% UV-absorber as described in Table 2;0-30% X

The cosmetic preparation according to the invention is distinguished byexcellent protection of human skin against the damaging effect ofsunlight.

EXAMPLES Preparation of the Samples for the Determination of thePhotostability

2% of the compound of formula

(Uvinul A Plus),

5% of the compound of formula

and

3% of the compound of formula

are dissolved in a cosmetic carrier.

This composition (A) is applied on rough quarz-plates (2 μl/cm²).

The times of irradiation are

-   -   0 h (no irradiation),    -   1 h (5 MED),    -   2 h (10 MED),    -   4 h (20 MED) and    -   10 h (50 MED)        with an Altas CPS+ sunlight simulator. For sufficient statistics        8 plates per time (x MED) are prepared. After irradiation, the        samples can be recovered completely with a defined amount (5 ml)        of a solvent (tetrahydrofurane).

HPLC:

The recovery of the UV-absorber was analyzed via HPLC:

column: Hypersil ODS 5 μm, 250 mm×4 mm

Solvent A: Water+2 g11 TBAHS

Solvent B: Acetonitrile/THF 9:1+2 g/l TBAHS

temperature: 35° C.

wavelength: 354 nm (for Detection of the compound of formula (101))

For comparison, the experiment is carried out in the same manner, butwith a preparation comprising only

2% of the compound of formula (101) and3% of the compound of formula (103) without the compound of formula(102) (=B).

The results: are listed in Table 2:

TABLE 3 Irradiation of UV absorber Compositions HPLC Recovery of thecompound of formula (101) Irradiation Composition A Composition B Noirradiation 100% 100%  5 MED 97% 82% 10 MED 92% 74% 20 MED 82% 46% 50MED 49% 1% MED = Minimal Erythema Dose Composition A: 2% of the UVabsorber of formula (101) 3% of the UV absorber of formula (103) 5% ofthe UV absorber of formula (102) Composition B: 2% of the UV absorber offormula (101) 3% of the UV absorber of formula (103)

The results in Table 2 clearly demonstrate that the addition of thediphenylacrylate UV absorber of formula (102) (=Octocrylene) stabilizesthe 2-hydroxybenzophenone UV absorber of formula (101) (=Uvinul A Plus)in a UV absorber composition which additionally comprises a UV absorberof formula (103 (=Parsol 1789; Avobenzone)

1. A method for improving the UV stability of a cosmetic ordermatological composition comprising adding to said composition aneffective photo-stabilizing amount of a UV filter combination whereinsaid combination is (a) a stabilizing agent selected from the groupconsisting of benzylidene camphor derivative (a₂); an organosiloxanecomprising benzalemalonate groups (a₃), a fluoren derivative (a₄), anaphthalene dicarboxylic acid derivative (a₅), a natural occurringstabilizer (a₆); and a phenolic antioxidant (a₇); (b) at least onedibenzoylmethane derivative; and (c) at least one specificamino-substituted 2-hydroxybenzophenone derivative.
 2. A methodaccording to claim 1 wherein the benzylidene camphor derivative (a2) isp-methylbenzylidene camphor.
 3. A method according to claim 1, whereinthe organosiloxane comprising benzalemalonate groups (a₃) corresponds tothe formula

wherein R is C₁-C₁₀alkyl; phenyl; or 3,3,3-trifluoropropyl, at least 80%of the number of the R radicals being methyl radicals; r is an integerfrom 0 to 200; s is an integer from 0 to 50; u is an integer from 1 to20; t is an integer from 0 to 20; wherein t+u is equal to or greaterthan 3; and A and/or B is a benzalemalonate radical.
 4. A methodaccording to claim 1, wherein the fluorein derivative (a₄) is selectedfrom the group consisting of derivatives ofcyano(9H-fluoren-9-ylidene)acetic acid, and diesters and polyesters of9H-fluoren-ylidenemalonic acid.
 5. A method according to claim 1,wherein the naphthalene dicarboxylic acid derivative (a₅) corresponds tothe formula

wherein R₁ is a radical of formula

k is 1 to 13; and R₂ is selected from the group consisting of a compoundof formula (4a), or C₁-C₂₂alkyl.
 6. A method according to claim 1,wherein the natural occurring stabilizer (a₆) is selected from the groupconsisting dragosine, green tea concentrate and grape seed extract.
 7. Amethod according to claim 1 wherein the stabilizing agent (a) is used ina concentration from 1 to 10 weight % based on total weight of thecosmetic or dermatological composition.
 8. A method according to claim 1wherein the dibenzoylmethane derivative (b) is4-tert-butyl-4′-methoxydibenzoylmethane.
 9. A method according to claim1 wherein the 2-hydroxybenzophenone derivative (c) corresponds toformula

wherein R₁ and R₂, independently from each other are hydrogen;C₁-C₃₀alkyl; C₂-C₁₀alkenyl; C₃-C₁₀ cycloalkyl; or C₃-C₁₀cycloalkenyl; orR₁ and R₂ together form, with the nitrogen atom to which they arebonded, a 5- or 6-membered heterocyclic ring member; R₃ and R₄,independently from each other, are each C₁-C₂₀alkyl; C₂-C₁₀alkenyl;C₃-C₁₀cycloalkyl; C₃-C₁₀cycloalkenyl; C₁-C₁₂alkoxy;(C₁-C₂₀)alkoxycarbonyl; C₁-C₁₂alkylamino; di(C₁-C₁₂)alkylamino; an arylor a heteroaryl radical which is optionally substituted; or awater-solubilizing substituent selected from a carboxylate group, asulfonate group or an ammonium residue; X is hydrogen; —COOR₅; or—CONR₆R₇; R₅, R₆ and R₇, independently from each other, are hydrogen;C₁-C₂₀alkyl; C₂-C₁₀alkenyl; C₃-C₁₀cycloalkyl; C₃-C₁₀cycloalkenyl,—(Y′O)₀—Z′; or aryl; Y′ is —(CH₂)₂—; —(CH₂)₃—; —(CH₂)₄—; or—CH—(CH₃)—CH₂—; Z′ is —CH₂—CH₃; —CH₂—CH₂CH₃; —CH₂CH₂—CH₂—CH₃ or—CH(CH₃)—CH₃; n is an integer from 0 to 3; and o is an integer from 1 to2.
 10. A method according to claim 10, wherein the 2-hydroxybenzophenonederivative (c) corresponds to formula

wherein R₁ and R₂, independently from each other, are hydrogen; orC₁-C₃alkyl; or together form, with the nitrogen atom to which they arebonded, a 5- or 6-membered heterocyclic ring member; and R₅ is hydrogen;C₁-C₅alkyl; or a C₃-C₆cycloalkyl.
 11. A method according to claim 10,wherein the 2-hydroxybenzo-phenone derivative (c) corresponds to formula


12. A method according to claim 1 wherein the cosmetic or dermatologicalcomposition comprises at least 1.0 to 10 weight % of a stabilizing agent(a) as defined in claim 1 based on total weight of said composition, 2.0to 5 weight % of a dibenzoylmethane derivative (b) based on total weightof said composition; and 0.3 to 10 weight % of an amino-substituted2-hydroxybenzophenone derivative (c) based on total weight of saidcomposition.
 13. A cosmetic or dermatological composition comprising atleast 1.0 to 10 weight % of a stabilizing agent (a) as defined in claim1 based on total weight of said composition; 2.0 to 5 weight % of adibenzoylmethane derivative UV filter (b) based on total weight of saidcomposition; and 0.3 to 10 weight % of an amino-substituted2-hydroxybenzophenone derivative UV filter (c) based on total weight ofsaid composition.